高等有机化学

1、_+_+_2s2pz2sp3OHHHHOHHHH_+OHHHH_+主要的贡献结构次要的贡献结构重要的贡献结构HNO2CH3OA_Cl.Cl.Cl.+. _Cl.+._Cl.+._n3. 参与共振的所有原子，即被非定域电子所参与共振的所有原子，即被非定域电子所涉及的原子，必须位于同一平面或近似同一涉及的原子，必须位于同一平面或近似同一平面。平面。n例如，丙烯基正离子采取平面的几何形状，例如，丙烯基正离子采取平面的几何形状，因为平面结构能使三个因为平面结构能使三个p轨道取得最大的重叠。轨道取得最大的重叠。n4. 共振结构必须具有相同数目的未配对电子共振结构必须具有相同数目的未配对电子n如果两个未配

2、对电子的自旋相同，则（如果两个未配对电子的自旋相同，则（II）式为双游离基，（式为双游离基，（II）式与（）式与（I）式所含有的）式所含有的未配对电子数目不同，因此（未配对电子数目不同，因此（II）式不是乙）式不是乙烯的共振结构。烯的共振结构。C C HHHHC C HHHH(I)(II).C HC HC HC CC CC CC OC OH HC CO OClClBrBrIIC HN HO HClHBrHIHC CC CN NC OC OC NH3CHCH3CH2HH2C CHHH2C CHCH2HPhCH2HH2NHCH3NHHCH3OHCH3CH3C2H5CH3(CH3)2CH CH3Ph

3、CH2CH3H5C2C2H5(CH3)2CH CH(CH3)2H2C CH2HC CHH3CFH3C ClH3CBrH3CIH3CIRCO2H + H2ORCO2- + H3O+ +2 +_2_环丁二烯苯 +2 +_2_环丁二烯苯H3COHHHHOCH3HHH3COHHCH2CH3HOCH3HCH2CH3SOPH3CH2CH2CCH3PhH2CNCH2CHPhCH3CH2+HOH2CCHOHO HHOH2CCHOH OHCCHOCH2OHHOHCHOOHHCH2OHCCHOCH2OHHOHCHOHHOCH2OHDD-(+)-甘油醛L-(-)-甘油醛LCO2HHH2NCH2SHCCHOCH2OH

4、HOHCHOOHHCH2OHDR-甘油醛L-半光氨酸R-半光氨酸CCCHHO2CHCO2HR-(-)- 戊二烯二酸S-（+）-螺环3，3-庚-1，5-二烯H3CH3CHHH3CHH3CHHH3CHH3CHOOHHHHOH2CCHOHOHHOHHOH2CCHOHOHHHOHOH2CCHOHHHOHOHOH2CCHO2R,3R2S,3S2S,3R2R,3S非对映异构体非对映异构体非对映异构体对映异构体非对映异构体2,3,4-三羟基丁醛中的立体异构关系(H3C)2HCCO2HHPh(H3C)2HCCO2HPhHHNH2CH3Ph(H3C)2HCCO2HPhHR-(-)S-(+)外消旋混合物R-(+)

5、非对映异构的羧酸铵盐（R-酸，R-胺和S-酸，R-胺）的混合物，从乙醇-水中重结晶重结晶后的产物：R，R盐从滤液中回收的盐富集了的S，R盐酸化酸化R-(-)-酸部分拆分的S-（+）-酸OPhOOPhOPhCat*O*+CH2CHOHTi(OR)4,t-BuOOHCH2CHOH(+)diisopropyl tartrate37% yield recovered, 95%e.e.OHOCH3NH2CO2HH+CO2OCH3H2N+racemicL-valine27% yield,96% d.e.CHCH3O2CCH3CHCH3OHRhizopus nigricansR-enantiomer,98%

6、e.e.at 28% conversionOCO2C2H5PhCH2OCO2C2H5PhCH2OOHBakers yeast38% yield, 82% d.e., 84% e.e.(CH2)8OHHH3C(H2C)7H(CH2)8OHHHH3C(H2C)7CH3CO3HCH3CO3HOHHH3C(H2C)7HO(H2C)8OHH3C(H2C)7HHO(H2C)8OSO2C6H4pCH3H3CH3C(H2C)5HOSO2C6H4pCH3H3CH3C(H2C)5HCH3CO2-CH3CO2-H3CO2CCH3H(CH2)5CH3H3CO2CHH3C(CH2)5CH3BrHPhH3CPhHKOCH

7、2CH3PhHH3CPhBrHPhH3CHPhKOCH2CH3HPhH3CPh苏型赤型；HN(CH3)2PhHH3CCH3-OCH3H3CPhHHN(CH3)2PhCH3H3CH-OHH3CPhCH3+115+苏型赤型125;PhOCH2ClHHHOPhHHOPhHn-BuLi /乙醚+(26%)(14%)PhCH3CHOHCH3MgIPhCH3HOHCH3HPhCH3HOHHCH3+赤型（67%）苏型（33%）O(H3C)3CLiAlH4(H3C)3CHOH(H3C)3COHH+(90%)(10%)PhCH3ClHOH-HOCH3HPhPhCH3OHH+C XR1R2R3C+R1R2R3-X-Nu-C NuR1R2R3+CR1R2R3NuPure enantiomerachiral intermediateracemic productHOOHH HHOOHD HHOOHH DHOOHHHHOOHHDHOOHDHR-1-氘-1,3-丙二醇S-